Pattern forming method as well as production methods for processed substrate, optical component, circuit board, electronic component and imprint mold

ABSTRACT

A pattern is formed on a substrate with a layer of a curable composition (A 1 ) containing a component (a 1 ) serving as a polymerizable compound on a surface of the substrate, then dispensing droplets of a curable composition (A 2 ) containing at least a component (a 2 ) serving as a polymerizable compound dropwise discretely onto the layer of the curable composition (A 1 ), subsequently sandwiching a mixture layer of the curable composition (A 1 ) and the curable composition (A 2 ) between a mold having a pattern and the substrate, then irradiating the mixture layer with light to cure the layer, and releasing the mold from the mixture layer after the curing, a contact angle of a composition of components of the curable composition (A 1 ) except a solvent of the curable composition (A 1 ) with respect to a surface of the mold being 10° or less.

This application claims the benefit of U.S. Provisional PatentApplication No. 62/315,727, filed Mar. 31, 2016, which is herebyincorporated by reference herein in its entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a pattern forming method, a method ofproducing a processed substrate, a method of producing an opticalcomponent, a method of producing a circuit board, a method of producingan electronic component, and a method of producing an imprint mold.

Description of the Related Art

There has been a growing requirement for miniaturization in asemiconductor device, a MEMS, or the like, and hence a photo-nanoimprinttechnology has been attracting attention as a microfabricationtechnology.

In the photo-nanoimprint technology, a photocurable composition (resist)is cured in a state in which a mold having a fine groove/land patternformed on its surface is pressed against a substrate (wafer) havingapplied thereto the photocurable composition. Thus, the groove/landpattern of the mold is transferred onto the cured film of thephotocurable composition and hence the pattern is formed on thesubstrate. According to the photo-nanoimprint technology, a finestructural body of the order of several nanometers can be formed on thesubstrate.

A photo-nanoimprint technology disclosed in Japanese Patent No. 4791357is described with reference to FIGS. 1A through 1F (including FIGS. 1DAand 1FA). First, a liquid resist 102 is dispensed dropwise discretelyonto a pattern formation region on a substrate 101 by using an inkjetmethod (arranging step (1), FIGS. 1A through 1C). Droplets of the resist102 dispensed dropwise spread on the substrate 101 as indicated byarrows 104 showing the direction in which droplets spread, and thephenomenon is called prespread (FIG. 1C). Next, the resist 102 is moldedwith a mold 105 that has a pattern formed thereon and is transparent toirradiation light 106 to be described later (mold contacting step (2),FIGS. 1D and 1DA). In the mold contacting step, the droplets of theresist 102 spread over the entire region of a gap between the substrate101 and the mold 105 as indicated by the arrows 104 showing thedirection in which droplets spread (FIG. 1D). The phenomenon is calledspread. In addition, in the mold contacting step, the resist 102 isfilled into a groove portion on the mold 105 as indicated by the arrows104 showing the direction in which droplets spread by the capillaryphenomenon (FIG. 1DA). The filling phenomenon is called fill. A timeperiod required for the spread and the fill to be completed is called afilling time. After the completion of the filling of the resist 102, theresist 102 is cured by being irradiated with irradiation light 106(light irradiating step (3), FIG. 1E), and then the substrate 101 isreleased from the mold 105 (releasing step (4), FIGS. 1F and 1FA). Theperformance of those steps results in the formation of a photocured film107 having a predetermined pattern shape (FIG. 1F) on the substrate 101.

SUMMARY OF THE INVENTION

The photo-nanoimprint technology disclosed in Japanese Patent No.4791357 has involved a problem in that a time period (filling time) fromthe initiation of the contact of the mold to the completion of thespread and the fill is long, and hence throughput is low.

An object of the present invention is to provide a pattern formingmethod having a short filling time, in other words, high throughput.

A pattern forming method according to one embodiment of the presentinvention includes in the following order:

an arranging step (1) of arranging a layer formed of a curablecomposition (A1) containing at least a component (a1) serving as apolymerizable compound on a surface of a substrate;

a dispensing step (2) of dispensing droplets of a curable composition(A2) containing at least a component (a2) serving as a polymerizablecompound dropwise discretely onto the layer formed of the curablecomposition (A1);

a mold contacting step (3) of sandwiching a mixture layer obtained bypartially mixing the curable composition (A1) and the curablecomposition (A2) between a mold having a pattern and the substrate;

a light irradiating step (4) of irradiating the mixture layer with lightfrom the side of the mold to cure the layer; and

a releasing step (5) of releasing the mold from the mixture layer afterthe curing,

a contact angle of a composition of components of the curablecomposition (A1) except a solvent with respect to a surface of the moldbeing 10° or less.

According to the present invention, there can be provided the patternforming method having high throughput.

Further features of the present invention will become apparent from thefollowing description of exemplary embodiments with reference to theattached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, 1B, 1C, 1D, 1DA, 1E, 1F and 1FA are schematic sectional viewsfor illustrating a precedent for a photo-nanoimprint technology.

FIGS. 2A, 2B, 2C, 2D, 2E, 2F and 2G are schematic sectional views forillustrating a SST-NIL technology.

DESCRIPTION OF THE EMBODIMENTS

An embodiment of the present invention is described in detail below withreference to the drawings as appropriate. However, the present inventionis not limited to the embodiment to be described below. Appropriatemodifications, improvements, and the like of the embodiment to bedescribed below that do not deviate from the gist of the presentinvention and are based on the ordinary knowledge of a person skilled inthe art are also included in the scope of the present invention. Inaddition, a component (a) contained in the curable composition (A1) iswritten as a component (a1), and a component (a) contained in thecurable composition (A2) is written as a component (a2). The sameapplies to a component (b) through (d).

[Curable Composition]

Curable compositions (A1) and (A2) according to this embodiment are eacha composition containing at least a component (a) serving as apolymerizable compound. The curable compositions according to thisembodiment may each further contain a component (b) serving as aphotopolymerization initiator, a component (c) serving as anon-polymerizable compound, and a component (d) serving as a solvent.

In addition, the term “cured film” as used herein means a film obtainedby polymerizing and curing a curable composition on a substrate. Theshape of the cured film is not particularly limited, and the film mayhave a pattern shape on its surface.

Each component is hereinafter described in detail.

<Component (a): Polymerizable Compound>

The component (a) is a polymerizable compound. The polymerizablecompound as used herein is a compound that reacts with a polymerizingfactor (such as a radical) generated from the component (b) serving as aphotopolymerization initiator to form a film formed of a polymercompound by a chain reaction (polymerization reaction).

As such polymerizable compound, there is given, for example, a radicalpolymerizable compound. The component (a) serving as a polymerizablecompound may be formed of only one kind of polymerizable compound or aplurality of kinds of polymerizable compounds.

It is preferred that the radical polymerizable compound be a compoundhaving one or more acryloyl groups or methacryloyl groups, that is, a(meth)acrylic compound. Therefore, it is preferred that the curablecompositions according to this embodiment each contain the (meth)acryliccompound as the component (a), it is more preferred that a maincomponent for the component (a) be the (meth)acrylic compound, and it ismost preferred that the entirety of the component (a) be the(meth)acrylic compound. The phrase “a main component for the component(a) is the (meth)acrylic compound” described herein means that the(meth)acrylic compound accounts for 90 wt % or more of the component(a).

When the radical polymerizable compound includes a plurality of kinds ofcompounds each having one or more acryloyl groups or methacryloylgroups, the compound preferably contains a monofunctional (meth)acrylicmonomer and a polyfunctional (meth)acrylic monomer. This is because thecombination of the monofunctional (meth)acrylic monomer and thepolyfunctional (meth)acrylic monomer provides a cured film having a highmechanical strength.

Monofunctional (meth)acrylic compounds having one acryloyl group ormethacryloyl group are exemplified by, but not limited to, phenoxyethyl(meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate,2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl(meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate,EO-modified p-cumylphenyl (meth)acrylate, 2-bromophenoxyethyl(meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate,2,4,6-tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy(meth)acrylate, PO-modified phenoxy (meth)acrylate, polyoxyethylenenonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl(meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate,dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate,cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate,ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate,butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate,t-butyl (meth)acrylate, pentyl (meth) acrylate, isoamyl (meth)acrylate,hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth) acrylate,isooctyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, nonyl(meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl(meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, isostearyl (meth)acrylate, benzyl (meth) acrylate,tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxy polypropylene glycol(meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl(meth)acrylamide, and N,N-dimethylaminopropyl (meth)acrylamide.

Examples of commercial products corresponding to the monofunctional(meth)acrylic compounds include, but not limited to: Aronix (trademark)M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, and M156(all of which are manufactured by Toagosei Co., Ltd); MEDOL10, MIBDOL10,CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, andViscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, and#2150 (all of which are manufactured by Osaka Organic Chemical IndustryLtd.); Light Acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL,PO-A, P-200A, NP-4EA, and NP-8EA, and Epoxy Ester M-600A (all of whichare manufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD (trademark)TC110S, R-564, and R-128H (all of which are manufactured by NipponKayaku Co., Ltd.); NK Ester AMP-10G and AMP-20G (both of which aremanufactured by Shin-Nakamura Chemical Co., Ltd.); FA-511A, 512A, and513A (all of which are manufactured by Hitachi Chemical Co., Ltd.); PHE,CEA, PHE-2, PHE-4, BR-31, BR-31M, and BR-32 (all of which aremanufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); VP (manufactured byBASF); and ACMO, DMAA, and DMAPAA (all of which are manufactured byKohjin Co., Ltd.).

In addition, polyfunctional (meth)acrylic compounds having two or moreacryloyl groups or methacryloyl groups are exemplified by, but notlimited to, trimethylolpropane di(meth)acrylate, trimethylolpropanetri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate,PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modifiedtrimethylolpropane tri(meth)acrylate, dimethyloltricyclodecanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate,1,3-adamantane dimethanol di(meth)acrylate,tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate,tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecanedi(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, EO-modified2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified2,2-bis(4-((meth)acryloxy)phenyl)propane, and EO,PO-modified2,2-bis(4-((meth)acryloxy)phenyl)propane.

Examples of commercial products corresponding to the polyfunctional(meth)acrylic compounds include, but not limited to: Upimer (trademark)UV SA1002 and SA2007 (both of which are manufactured by MitsubishiChemical Corporation); Viscoat #195, #230, #215, #260, #335HP, #295,#300, #360, #700, GPT, and 3PA (all of which are manufactured by OsakaOrganic Chemical Industry Ltd.); Light Acrylate 4EG-A, 9EG-A, NP-A,DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, and DPE-6A (all of which aremanufactured by Kyoeisha Chemical Co., Ltd.); KAYARAD (trademark)PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, and -120, and HX-620,D-310, and D-330 (all of which are manufactured by Nippon Kayaku Co.,Ltd.); Aronix (trademark) M208, M210, M215, M220, M240, M305, M309,M310, M315, M325, and M400 (all of which are manufactured by ToagoseiCo., Ltd); and Lipoxy (trademark) VR-77, VR-60, and VR-90 (all of whichare manufactured by Showa Highpolymer Co., Ltd.).

In the above-mentioned compound group, the term “(meth)acrylate” meansan acrylate or a methacrylate having an alcohol residue equal to theacrylate. The term “(meth)acryloyl group” means an acryloyl group or amethacryloyl group having an alcohol residue equal to the acryloylgroup. The abbreviation “EO” refers to ethylene oxide, and the term“EO-modified compound A” means a compound in which a (meth)acrylic acidresidue and an alcohol residue of the compound A are bonded to eachother through a block structure of an ethylene oxide group. Further, theabbreviation “PO” refers to propylene oxide, and the term “PO-modifiedcompound B” means a compound in which a (meth)acrylic acid residue andan alcohol residue of the compound B are bonded to each other through ablock structure of a propylene oxide group.

The blending ratio of the component (a1) serving as a polymerizablecompound in the curable composition (A1) is desirably 50 wt % or moreand 100 wt % or less with respect to the total weight of the component(a1), the component (b1), the component (c1), and the component (d1),i.e., the total weight of the components of the curable composition (A1)except the component (e1) serving as a solvent. In addition, theblending ratio is preferably 80 wt % or more and 100 wt % or less, morepreferably 90 wt % or more and 100 wt % or less.

When the blending ratio of the component (a1) serving as a polymerizablecompound in the curable composition (A1) is set to 50 wt % or more withrespect to the total weight of the component (a1), the component (b1),the component (c1), and the component (d1), a cured film to be obtainedcan be turned into a cured film having some degree of mechanicalstrength.

The blending ratio of the component (a2) serving as a polymerizablecompound in the curable composition (A2) is desirably 50 wt % or moreand 99.9 wt % or less with respect to the total weight of the component(a2), the component (b2), the component (c2), and the component (d2),i.e., the total weight of the components of the curable composition (A2)except the component (e2) serving as a solvent. In addition, theblending ratio is preferably 80 wt % or more and 99 wt % or less, morepreferably 90 wt % or more and 98 wt % or less.

When the blending ratio of the component (a2) serving as a polymerizablecompound in the curable composition (A2) is set to 50 wt % or more withrespect to the total weight of the component (a2), the component (b2),the component (c2), and the component (d2), a cured film to be obtainedcan be turned into a cured film having some degree of mechanicalstrength.

In addition, as described below, it is preferred that the curablecomposition (A1) contain the component (e1). The blending ratio of thecomponent (a1) in the curable composition (A1) is desirably 0.01 wt % ormore and 10 wt % or less with respect to the total weight of thecomponents of the curable composition (A1) containing the component (e1)serving as a solvent.

<Component (b): Photopolymerization Initiator>

The component (b) is a photopolymerization initiator.

The photopolymerization initiator as used herein is a compound thatdetects light having a predetermined wavelength to generate theabove-mentioned polymerizing factor (radical). Specifically, thephotopolymerization initiator is a polymerization initiator (radicalgenerator) that generates a radical with light (a radiation, e.g., aninfrared ray, a visible ray, an ultraviolet ray, a far ultraviolet ray,an X-ray, or a charged particle ray such as an electron beam).

The component (b) may be formed of one kind of photopolymerizationinitiator or a plurality of kinds of photopolymerization initiators.

Examples of the radical generator include, but not limited to:2,4,5-triarylimidazole dimers that may have a substituent such as a2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, a2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, a2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and a 2-(o- orp-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone andbenzophenone derivatives such asN,N′-tetramethyl-4,4′-diaminobenzophenone (Michler's ketone),N,N′-tetraethyl-4,4′-diaminobenzophenone,4-methoxy-4′-dimethylaminobenzophenone, 4-chlorobenzophenone,4,4′-dimethoxybenzophenone, and 4,4′-diaminobenzophenone; α-aminoaromatic ketone derivatives such as2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one;quinones such as 2-ethylanthraquinone, phenanthrenequinone,2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone,2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone,9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoinmethyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin andbenzoin derivatives such as methylbenzoin, ethylbenzoin, andpropylbenzoin; benzyl derivatives such as benzyl dimethyl ketal;acridine derivatives such as 9-phenylacridine and1,7-bis(9,9′-acridinyl)heptane; N-phenylglycine derivatives such asN-phenylglycine; acetophenone and acetophenone derivatives such as3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone andthioxanthone derivatives such as diethylthioxanthone,2-isopropylthioxanthone, and 2-chlorothioxanthone; acylphosphine oxidederivatives such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide,bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, andbis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; oximeester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzoyloxime)] and ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime);xantone; fluorenone; benzaldehyde; fluorene; anthraquinone;triphenylamine; carbazole;1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; and2-hydroxy-2-methyl-1-phenylpropan-1-one.

Examples of commercial products corresponding to the radical generatorinclude, but not limited to, Irgacure 184, 369, 651, 500, 819, 907, 784,and 2959, CGI-1700, -1750, and -1850, CG24-61, Darocur 1116 and 1173,Lucirin (trademark) TPO, LR8893, and LR8970 (all of which aremanufactured by BASF), and Ubecryl P36 (manufactured by UCB).

Of those, the component (b) is preferably an acylphosphine oxide-basedpolymerization initiator. The acylphosphine oxide-based polymerizationinitiator is, of the examples described above, an acylphosphine oxidecompound such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide,bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, orbis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide.

The blending ratio of the component (b) serving as a photopolymerizationinitiator in the curable composition (A1) and (A2) is desirably 0.1 wt %or more and 50 wt % or less with respect to the total weight of thecomponent (a), the component (b), and the component (c) to be describedlater, i.e., the total weight of the components of the curablecomposition (A1) or (A2) except the component (d) serving as a solvent.In addition, the blending ratio is preferably 0.1 wt % or more and 20 wt% or less, more preferably 1 wt % or more and 10 wt % or less.

When the blending ratio of the component (b) is set to 0.1 wt % or morewith respect to the total weight of the component (a), the component(b), and the component (c), the curing rate of the composition increasesand hence reaction efficiency can be improved. In addition, when theblending ratio of the component (b) is set to 50 wt % or less withrespect to the total weight of the component (a), the component (b), andthe component (c), a cured film to be obtained can be turned into acured film having some degree of mechanical strength.

<Component (c): Non-Polymerizable Compound>

The curable compositions (A1) and (A2) according to this embodiment caneach further contain the component (c) serving as a non-polymerizablecompound in addition to the component (a) and the component (b)described in the foregoing in accordance with various purposes to theextent that the effects of the present invention are not impaired. Suchcomponent (c) is, for example, a compound that is free of apolymerizable functional group such as a (meth)acryloyl group, and isfree of an ability to sense light having a predetermined wavelength togenerate the polymerizing factor (radical). Examples thereof include asensitizer, a hydrogen donor, an internal addition-type release agent, asurfactant, an antioxidant, a polymer component, and other additives.Two or more kinds of the compounds may be incorporated as the component(c).

The sensitizer is a compound to be appropriately added for the purposeof accelerating a polymerization reaction or enhancing a reactionconversion ratio. As the sensitizer, there is given, for example, asensitizing dye.

The sensitizing dye is a compound that is excited by absorbing lighthaving a specific wavelength to interact with the component (b) servingas a polymerization initiator. The term “interaction” described hereinrefers to, for example, the transfer of energy or an electron from thesensitizing dye in an excited state to the component (b) serving as apolymerization initiator.

Specific examples of the sensitizing dye include, but not limited to, ananthracene derivative, an anthraquinone derivative, a pyrene derivative,a perylene derivative, a carbazole derivative, a benzophenonederivative, a thioxanthone derivative, a xanthone derivative, a coumarinderivative, a phenothiazine derivative, a camphorquinone derivative, anacridine-based dye, a thiopyrylium salt-based dye, a merocyanine-baseddye, a quinoline-based dye, a styrylquinoline-based dye, aketocoumarin-based dye, a thioxanthene-based dye, a xanthene-based dye,an oxonol-based dye, a cyanine-based dye, a rhodamine-based dye, and apyrylium salt-based dye.

One kind of the sensitizers may be used alone, or two or more kindsthereof may be used as a mixture.

The hydrogen donor is a compound capable of reacting with an initiationradical generated from the component (b) serving as a polymerizationinitiator or the radical of a polymerization growth terminal to generatea more reactive radical. The hydrogen donor is preferably added when thecomponent (b) serving as a polymerization initiator is a photoradicalgenerator.

Specific examples of such hydrogen donor include, but not limited to,amine compounds such as n-butylamine, di-n-butylamine, allylthiourea,triethylamine, triethylenetetramine, a4,4′-bis(dialkylamino)benzophenone, N,N-dimethylaminobenzoic acid ethylester, N,N-dimethylaminobenzoic acid isoamyl ester,pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine,and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and amercaptopropionic acid ester, sulfur compounds, such ass-benzylisothiuronium-p-toluenesulfinate, and phosphorous compounds,such as tri-n-butylphosphine.

One kind of the hydrogen donors may be used alone, or two or more kindsthereof may be used as a mixture. In addition, the hydrogen donor mayhave a function as a sensitizer.

The internal addition-type release agent can be added to each of thecurable compositions for the purpose of reducing an interfacial bondingforce between a mold and a resist, i.e., reducing a release force in areleasing step to be described later. The term “internal addition-type”as used herein means that the release agent is added to the curablecomposition prior to the step of arranging the curable composition.

For example, surfactants such as a silicone-based surfactant, afluorine-based surfactant, and a hydrocarbon-based surfactant, can eachbe used as the internal addition-type release agent. In the presentinvention, the internal addition-type release agent is free ofpolymerizability.

Examples of the fluorine-based surfactant include a polyalkylene oxide(such as polyethylene oxide or polypropylene oxide) adduct of an alcoholhaving a perfluoroalkyl group, and a polyalkylene oxide (such aspolyethylene oxide or polypropylene oxide) adduct of perfluoropolyether.The fluorine-based surfactant may have, for example, a hydroxyl group,an alkoxy group, an alkyl group, an amino group, or a thiol group onpart (for example, as a terminal group) of its molecular structure.

As the fluorine-based surfactant, a commercial product may be used.Examples of the commercial product include MEGAFACE (trademark) F-444,TF-2066, TF-2067, and TF-2068 (all of which are manufactured by DICCorporation), Fluorad FC-430 and FC-431 (both of which are manufacturedby Sumitomo 3M Limited), Surflon (trademark) S-382 (manufactured byAGC), EFTOP EF-122A, 122B, and 122C, EF-121, EF-126, EF-127, and MF-100(all of which are manufactured by Tohkem Products Corp.), PF-636,PF-6320, PF-656, and PF-6520 (all of which are manufactured by OMNOVASolutions), UNIDYNE (trademark) DS-401, DS-403, and DS-451 (all of whichare manufactured by Daikin Industries, Ltd.), and Ftergent (trademark)250, 251, 222F, and 208G (all of which are manufactured by NeosCorporation).

In addition, the internal addition-type release agent may be thehydrocarbon-based surfactant.

The hydrocarbon-based surfactant includes, for example, an alkyl alcoholpolyalkylene oxide adduct, in which an alkylene oxide having 2 to 4carbon atoms is added to an alkyl alcohol having 1 to 50 carbon atoms.

Examples of the alkyl alcohol polyalkylene oxide adduct include a methylalcohol ethylene oxide adduct, a decyl alcohol ethylene oxide adduct, alauryl alcohol ethylene oxide adduct, a cetyl alcohol ethylene oxideadduct, a stearyl alcohol ethylene oxide adduct, and a stearyl alcoholethylene oxide/propylene oxide adduct. The terminal group of the alkylalcohol polyalkylene oxide adduct is not limited to a hydroxyl group,which is simply produced by adding a polyalkylene oxide to an alkylalcohol. The hydroxyl group may be substituted with another substituent,for example, a polar functional group such as a carboxyl group, an aminogroup, a pyridyl group, a thiol group, or a silanol group, or ahydrophobic functional group such as an alkyl group or an alkoxy group.

As the alkyl alcohol polyalkylene oxide adduct, a commercial product maybe used. Examples of the commercial product include polyoxyethylenemethyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400,MP-550, and MP-1000) manufactured by Aoki Oil Industrial Co., Ltd.,polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct)(FINESURF D-1303, D-1305, D-1307, and D-1310) manufactured by Aoki OilIndustrial Co., Ltd., polyoxyethylene lauryl ether (lauryl alcoholethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki OilIndustrial Co., Ltd., polyoxyethylene cetyl ether (cetyl alcoholethylene oxide adduct) (BLAUNON CH-305 and CH-310) manufactured by AokiOil Industrial Co., Ltd., polyoxyethylene stearyl ether (stearyl alcoholethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730,and SR-750) manufactured by Aoki Oil Industrial Co., Ltd., randompolymerization-type polyoxyethylene polyoxypropylene stearyl ether(BLAUNON SA-50/50 1000R and SA-30/70 2000R) manufactured by Aoki OilIndustrial Co., Ltd., polyoxyethylene methyl ether (Pluriol (trademark)A760E) manufactured by BASF, and polyoxyethylene alkyl ethers (EMULGENSeries) manufactured by Kao Corporation.

Of those hydrocarbon-based surfactants, the alkyl alcohol polyalkyleneoxide adduct is preferred as the internal addition-type release agent,and a long-chain alkyl alcohol polyalkylene oxide adduct is morepreferred.

One kind of the internal addition-type release agents may be used alone,or two or more kinds thereof may be used as a mixture.

The blending ratio of the component (c) serving as a non-polymerizablecompound in each of the curable compositions is desirably 0 wt % or moreand 50 wt % or less with respect to the total weight of the component(a), the component (b), and the component (c) to be described later,i.e., the total weight of the components of the curable compositionsexcept the solvent. In addition, the blending ratio is preferably 0.1 wt% or more and 50 wt % or less, more preferably 0.1 wt % or more and 20wt % or less.

When the blending ratio of the component (c) is set to 50 wt % or lesswith respect to the total weight of the component (a), the component(b), and the component (c), a cured film to be obtained can be turnedinto a cured film having some degree of mechanical strength.

<Component (d): Solvent>

The curable compositions according to this embodiment may each contain acomponent (d) serving as a solvent. The component (d) is notparticularly limited as long as the component is a solvent thatdissolves the component (a), the component (b), and the component (c).The solvent is preferably a solvent having a boiling point at normalpressure of 80° C. or more and 200° C. or less. The solvent is morepreferably a solvent having at least one of an ester structure, a ketonestructure, a hydroxyl group, or an ether structure. The solvent isspecifically, for example, a single solvent selected from propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether,cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate, or amixed solvent of two or more kinds thereof.

The curable composition (A1) according to this embodiment preferablycontains the component (d1). This is because, as described later, a spincoating method is preferred as a method of applying the curablecomposition (A1) onto the substrate.

<Temperature at Time of Blending of Curable Composition>

When the curable compositions (A1) and (A2) of this embodiment areprepared, each component is mixed and dissolved under a predeterminedtemperature condition. Specifically, the preparation is performed in arange of from 0° C. or more to 100° C. or less.

<Viscosity of Curable Composition>

The curable compositions (A1) and (A2) according to this embodiment arepreferably liquid. This is because in a mold contacting step to bedescribed later, the spread and fill of the curable composition (A1)and/or the curable composition (A2) are quickly completed, in otherwords, a filling time is short.

The viscosity of the composition of the components of the curablecomposition (A1) except the component (d1) serving as a solventaccording to this embodiment at 25° C. is preferably 1 mPa·s or more and1,000 mPa·s or less. In addition, the viscosity is more preferably 1mPa·s or more and 500 mPa·s or less, still more preferably 1 mPa·s ormore and 100 mPa·s or less.

The viscosity of the composition of the components of the curablecomposition (A2) except the component (d2) serving as a solvent of thecurable composition (A2) according to this embodiment at 25° C. ispreferably 1 mPa·s or more and 100 mPa·s or less. In addition, theviscosity is more preferably 1 mPa·s or more and 50 mPa·s or less, stillmore preferably 1 mPa·s or more and 12 mPa·s or less.

When the viscosities of the curable compositions (A1) and (A2) are setto 100 mPa·s or less, spread and fill are quickly completed at the timeof the bringing of the curable compositions (A1) and (A2) into contactwith the mold (S. Reddy, R. T. Bonnecaze/Microelectronic Engineering,(2005) 60-70). In other words, when the curable compositions accordingto this embodiment are used, a photo-nanoimprint method can be performedat high throughput. In addition, a pattern defect due to a fillingfailure hardly occurs.

In addition, when the viscosities are set to 1 mPa·s or more,application unevenness hardly occurs at the time of the application ofthe curable compositions (A1) and (A2) onto the substrate. Further, whenthe curable compositions (A1) and (A2) are brought into contact with themold, the curable compositions (A1) and (A2) hardly flow out of an endportion of the mold.

<Surface Tension of Curable Composition>

With regard to the surface tension of each of the curable compositions(A1) and (A2) according to this embodiment, the surface tension of thecomposition of the components of the curable compositions (A1) and (A2)except the component (d) serving as a solvent at 23° C. is preferably 5mN/m or more and 70 mN/m or less. In addition, the surface tension ismore preferably 7 mN/m or more and 50 mN/m or less, still morepreferably 10 mN/m or more and 40 mN/m or less. In this case, as thesurface tension becomes higher, e.g., 5 mN/m or more, a strongercapillary force acts, and hence filling (the spread and the fill) iscompleted within a shorter time period at the time of the bringing ofthe curable composition (A1) and/or the curable composition (A2) intocontact with the mold (S. Reddy, R. T. Bonnecaze/MicroelectronicEngineering, 82 (2005) 60-70).

In addition, when the surface tension is set to mN/m or less, a curedfilm obtained by curing the curable compositions becomes a cured filmhaving surface smoothness.

In this embodiment, the surface tension of a composition of thecomponents of the curable composition (A1) except the component (d1)serving as a solvent is preferably higher than the surface tension of acomposition of the components of the curable composition (A2) except thecomponent (d2) serving as a solvent. This is because of the followingreason. Before the mold contacting step, the prespread of the curablecomposition (A2) is accelerated (droplets spread over a wide range) by aMarangoni effect to be described later, and hence a time period requiredfor spread in the mold contacting step to be described later isshortened. As a result, a filling time is shortened.

The Marangoni effect is a free surface movement phenomenon resultingfrom a local difference in surface tension between liquids (N.Imaishi/Int. J. Microgravity Sci. No. 31 Supplement 2014 (S5-S12)). Thedifference in surface tension, in other words, surface energy serves asa driving force to cause such diffusion that a liquid having a lowsurface tension covers a wider surface. In other words, when the curablecomposition (A1) having a high surface tension is applied to the entiresurface of the substrate and the curable composition (A2) having a lowsurface tension is dispensed dropwise, the prespread of the curablecomposition (A2) is accelerated.

<Contact Angle of Curable Composition>

With regard to the contact angle of each of the curable compositions(A1) and (A2) according to this embodiment, the contact angle of acomposition of the components of the curable compositions (A1) and (A2)except the component (d) serving as a solvent is preferably 0° or moreand 90° or less with respect to each of both the surface of thesubstrate and the surface of the mold. When the contact angle is morethan 90°, a capillary force acts in a negative direction (direction inwhich a contact interface between the mold and the curable compositionis shrunk) in a mold pattern or in a gap between the substrate and themold, and hence the composition is not filled. The contact angle isparticularly preferably 0° or more and 30° or less. As the contact anglebecomes lower, a stronger capillary force acts and hence a filling rateincreases (S. Reddy, R. T. Bonnecaze/Microelectronic Engineering, 82(2005) 60-70).

In the present invention, a contact angle of a composition of thecomponents of the curable composition (A1) except a component (d1)serving as a solvent with respect to a surface of the mold is set to be10° or less. The reason is described in detail in the paragraphdescribing the Pattern Forming Method.

The viscosity, the surface tension, and the contact angle of each of thecurable compositions (A1) and (A2) according to this embodiment can bechanged by addition of the component (d) serving as a solvent. However,the component (d) serving as a solvent may prevent curing of the curablecompositions (A1) and (A2). Accordingly, the viscosity, the surfacetension, and the contact angle of the compositions of the components ofthe curable compositions (A1) and (A2) except a component (d) serving asa solvent are used in this embodiment.

<Impurities Mixed in Curable Composition>

It is preferred that the curable compositions (A1) and (A2) according tothis embodiment each be free of impurities to the extent possible. Theterm “impurities” as used herein refers to components except thecomponent (a), the component (b), the component (c), and the component(d) described above.

Thus, it is preferred that the curable compositions according to thisembodiment each be obtained through a purification step. Thepurification step is preferably filtration using a filter or the like.

When the filtration using a filter is performed, specifically, it ispreferred that the component (a) and the component (b) described in theforegoing and additive components to be added as required be mixed, andthen the mixture be filtered with a filter having a pore diameter of,for example, 0.001 μm or more and 5.0 μm or less. It is more preferredthat the filtration using a filter be performed in a plurality of stagesor be repeated a plurality of times. In addition, the filtered liquidmay be filtered again. A plurality of filters having different porediameters may be used to perform the filtration. A filter made of, forexample, a polyethylene resin, a polypropylene resin, a fluororesin, ora nylon resin can be used as the filter to be used in the filtration.However, the filter is not particularly limited thereto.

Impurities such as particles, which are mixed in the curablecompositions, can be removed through such purification step. Thus, theimpurities such as the particles, can be prevented from formingunexpected unevenness in the cured film to be obtained after the curablecompositions are cured to cause a pattern defect.

When the curable compositions according to this embodiment are used forthe manufacture of a semiconductor integrated circuit, it is preferredto avoid the mixing of metal atom-containing impurities (metalimpurities) in the curable compositions to the extent possible in orderto prevent the operation of a product from being inhibited. In thiscase, the concentration of the metal impurities in the curablecompositions is preferably 10 ppm or less, more preferably 100 ppb orless.

[Pattern Forming Method]

Next, a pattern forming method according to this embodiment is describedwith reference to the schematic sectional views of FIGS. 2A through 2G.

The pattern forming method according to this embodiment is one mode ofthe photo-nanoimprint method. The pattern forming method of thisembodiment includes:

the first laying step (1) of laying the curable composition (A1) 202 ofthis embodiment described in the foregoing on the substrate 201;

the second laying step (2) of laying the curable composition (A2) 203 onthe layer of the curable composition (A1) 202;

the mold contacting step (3) of sandwiching the mixture layer obtainedby partially mixing the curable composition (A1) 202 and the curablecomposition (A2) 203 between the mold 205 having a pattern and thesubstrate 201;

the light irradiating step (4) of irradiating the mixture with theirradiation light 206 from the side of the mold 205 to cure the layer;and

the releasing step (5) of releasing the mold 205 from the cured film 207formed of the curable compositions after the curing.

A cured film obtained by the method of producing a cured film having apattern shape according to this embodiment is preferably a film having apattern having a size of 1 nm or more and 10 mm or less. In addition,the cured film is more preferably a film having a pattern having a sizeof 10 nm or more and 100 μm or less. In general, a pattern formingtechnology for producing a film having a pattern (uneven structure) of ananosize (1 nm or more and 100 nm or less) through the use of light iscalled a photo-nanoimprint method. The pattern forming method accordingto this embodiment uses the photo-nanoimprint method.

Each step is hereinafter described.

<First Laying Step (1)>

In this step (first laying step), as illustrated in FIGS. 2A and 2B, thecurable composition (A1) 202 according to this embodiment described inthe foregoing is laid (applied) onto the substrate 201 to form anapplied film.

The substrate 201 on which the curable composition (A1) 202 is to bearranged is a substrate to be processed, and a silicon wafer istypically used. A layer to be processed may be formed on the substrate201. Another layer may be further formed between the substrate 201 andthe layer to be processed. In addition, when a quartz substrate is usedas the substrate 201, a replica of a quartz imprint mold (mold replica)can be produced.

In the present invention, however, the substrate 201 is not limited tothe silicon wafer and the quartz substrate. The substrate 201 can bearbitrarily selected from substrates known as substrates forsemiconductor devices such as aluminum, a titanium-tungsten alloy, analuminum-silicon alloy, an aluminum-copper-silicon alloy, silicon oxide,and silicon nitride.

The adhesiveness of the surface of the substrate 201 (substrate to beprocessed) to be used or of the layer to be processed with each of thecurable compositions (A1) 202 and (A2) 203 may be improved by a surfacetreatment such as a silane coupling treatment, a silazane treatment, orthe formation of an organic thin film.

In this embodiment, as a method of arranging the curable composition(A1) 202 on the substrate 201 or the layer to be processed, there may beused, for example, an ink jet method, a dip coating method, an air knifecoating method, a curtain coating method, a wire bar coating method, agravure coating method, an extrusion coating method, a spin coatingmethod, or a slit scan method. In the present invention, a spin coatingmethod is particularly preferred.

When the curable composition (A1) 202 is arranged on the substrate 201or the layer to be processed by using the spin coating method, thecomponent (d1) serving as a solvent may be volatilized by performing abaking step as required.

The average thickness of the film of the curable composition (A1) 202,which varies depending on applications where the composition is used,is, for example, 0.1 nm or more and 10,000 nm or less, preferably 1 nmor more and 20 nm or less, particularly preferably 1 nm or more and 10nm or less.

<Second Laying Step (2)>

In this step (second laying step), as illustrated in FIGS. 2C and 2D,droplets of the curable composition (A2) 203 are preferably dispenseddropwise discretely and arranged on the layer of the curable composition(A1) 202. The inkjet method is particularly preferred as a method forthe arrangement. The droplets of the curable composition (A2) 203 aredensely arranged on a substrate 201 facing a region where grooveportions are densely present on the mold 205, and are sparsely arrangedon a substrate 201 facing a region where groove portions are sparselypresent. Thus, the thickness of a remaining film to be described latercan be controlled to a uniform value irrespective of the density of apattern on the mold 205.

In the present invention, as described in the foregoing, the droplets ofthe curable composition (A2) 203 arranged in this step (second layingstep) are quickly spread in the directions indicated by the arrows 204showing the direction in which droplets spread by the Marangoni effect(prespread). The inventors of the present invention have found that inthe course of the prespread, the curable composition (A1) 202 and thecurable composition (A2) 203 partially mix with each other, that theconcentration of the curable composition (A1) 202 is high in a boundaryregion between the droplets of the curable composition (A2) 203, andthat such behavior that the liquid film of the curable composition (A1)202 rises (FIG. 2D) is observed in the region. As a result of the riseof the liquid film of the curable composition (A1) 202, as illustratedin FIG. 2E, the curable composition (A1) 202 is brought into directcontact with the mold 205. In the region where the curable composition(A1) 202 is brought into direct contact with the mold 205, it isnecessary that the curable composition (A1) 202 itself be filled intothe mold pattern and cured to form a pattern. Accordingly, the inventorshave found that the contact angle of the curable composition (A1) 202with respect to the surface of the mold 205 needs to be set to 10° orless for quickly filling the curable composition (A1) 202 into the moldpattern by virtue of a capillary phenomenon.

In each of Japanese Patent Application Laid-Open No. 2011-159924,Japanese Patent Application Laid-Open No. 2011-168003, Japanese PatentApplication Laid-Open No. 2011-187824, and Japanese Patent ApplicationLaid-Open No. 2011-235571 serving as the prior art documents, there is adisclosure of one mode of a photo-nanoimprint method involving using twoor more kinds of different curable compositions while laying thecompositions. However, in each of the prior art documents, there is nodisclosure of such a mode that a lower layer is brought into directcontact with a mold 205.

<Mold Contacting Step (3)>

Next, as illustrated in FIG. 2E, the mold 205 having a template patternfor transferring a pattern shape is brought into contact with a layer ofa liquid obtained by partially mixing the curable composition (A1) 202and the curable composition (A2) 203, the liquid being formed in theprevious steps (first and second laying steps). Thus, a groove portionof a fine pattern on the surface of the mold 205 is filled with theliquid obtained by partially mixing the curable composition (A1) 202 andthe curable composition (A2) 203, and hence a liquid film filled intothe fine pattern of the mold 205 is obtained.

The mold 205 that is formed of an optically transparent material isdesirably used as the mold 205 considering the next step (lightirradiating step). Preferred specific examples of the material forforming the mold 205 include: glass, quartz, an optically transparentresin such as PMMA or a polycarbonate resin, a transparentmetal-deposited film, a flexible film made of polydimethylsiloxane orthe like, a photocured film, and a metal film. In the case of using theoptically transparent resin as the material for forming the mold 205, itis necessary to select a resin that does not dissolve in a componentcontained in the curable composition. Quartz is particularly preferredas the material for forming the mold 205 because of its small thermalexpansion coefficient and small pattern deformation.

The fine pattern on the surface of the mold 205 preferably has a patternheight of 4 nm or more and 200 nm or less.

As the pattern height becomes lower, the force by which the mold 205 ispeeled from the cured film 207 of a resist in the releasing step, i.e.,a release force reduces, and the number of release defects remaining ona mask side owing to the tearing-off of a resist pattern in associationwith the release reduces. Adjacent resist patterns are brought intocontact with each other by the elastic deformation of the resistpatterns due to an impact at the time of the peeling of the mold 205,and hence the resist patterns adhere to each other or are damaged insome cases. However, when the pattern height is about twice or less aslarge as a pattern width (an aspect ratio is 2 or less), there is a highpossibility that such inconveniences can be avoided. Meanwhile, when thepattern height is excessively low, the processing accuracy of thesubstrate 201 (substrate to be processed) is low.

The mold 205 may be subjected to a surface treatment before this step,which is a mold contacting step of the curable compositions (A1) 202 and(A2) 203 and the mold 205, so as to enhance the releasability betweenthe curable compositions (A1) 202 and (A2) 203 and the surface of themold 205. As a method for the surface treatment, there is given a methodinvolving forming a release agent layer by applying a release agent ontothe surface of the mold 205. In this case, examples of the release agentto be applied onto the surface of the mold 205 include a silicon-basedrelease agent, a fluorine-based release agent, a hydrocarbon-basedrelease agent, a polyethylene-based release agent, a polypropylene-basedrelease agent, a paraffin-based release agent, a montan-based releaseagent, and a carnauba-based release agent. For example, a commerciallyavailable application-type release agent such as OPTOOL (trademark) DSXmanufactured by Daikin Industries, Ltd. can be suitably used. One kindof the release agents may be used alone, or two or more kinds thereofmay be used in combination. Of those, fluorine-based andhydrocarbon-based release agents are particularly preferred.

A pressure to be applied to the curable compositions (A1) 202 and (A2)203 when the mold 205 and the curable compositions (A1) 202 and (A2) 203are brought into contact with each other in this step (mold contactingstep) as illustrated in FIG. 2E is not particularly limited. Thepressure is desirably set to 0 MPa or more and 100 MPa or less. Inaddition, the pressure is preferably 0 MPa or more and 50 MPa or less,more preferably 0 MPa or more and 30 MPa or less, still more preferably0 MPa or more and 20 MPa or less.

In the present invention, the prespread of the droplets of the curablecomposition (A2) 203 has progressed in the previous step (second layingstep), and hence the spread of the curable composition (A2) 203 in thisstep is quickly completed. In a boundary region between the droplets ofthe curable composition (A2) 203, the spread is finally completed andthe concentration of the curable composition (A1) 202 is high. However,as described in the foregoing, the contact angle of the curablecomposition (A1) 202 is low and hence the fill is quickly completed inthe region as well.

As described above, the spread and fill of the curable compositions (A1)202 and (A2) 203 are quickly completed in this step, and hence the timeperiod for which the mold 205, and the curable compositions (A1) 202 and(A2) 203 are brought into contact with each other can be set to beshort. In other words, the effects of the present invention is asfollows: many pattern forming steps can be completed within a short timeperiod, and hence high productivity is obtained. The time period forwhich the mold 205 and the compositions (A1) 202 and (A2) 203 arebrought into contact with each other, which is not particularly limited,is desirably set to, for example, 0.1 second or more and 600 seconds orless. In addition, the time period is preferably 0.1 second or more and3 seconds or less, particularly preferably 0.1 second or more and 1second or less. When the time period is shorter than 0.1 second, thefollowing tendency is observed: the spread and the fill becomeinsufficient, and hence many defects called nonfill defects occur.

The mold contacting step can be performed under any condition of an airatmosphere, a reduced pressure atmosphere, and an inert gas atmosphere.Of those atmospheres, a reduced pressure atmosphere or an inert gasatmosphere is preferred because an influence of oxygen or moisture on acuring reaction can be prevented. When this step is performed under aninert gas atmosphere, specific examples of the inert gas that can beused include nitrogen, carbon dioxide, helium, argon, variousfluorocarbon gases, and a mixed gas thereof. A preferred pressure whenthis step is performed under a particular gas atmosphere including anair atmosphere is 0.0001 atm or more and 10 atm or less.

The mold contacting step may be performed under an atmosphere containinga condensable gas (hereinafter referred to as “condensable gasatmosphere”). The term “condensable gas” as used herein refers to thefollowing gas: when the gas in the atmosphere is filled into a grooveportion of the fine pattern formed on the mold 205, and the gap betweenthe mold 205 and the substrate 201 together with the curablecompositions (A1) 202 and (A2) 203, the gas is condensed by a capillarypressure generated at the time of the filling to liquefy. Thecondensable gas is present as a gas in the atmosphere before the curablecompositions (A1) 202 and (A2) 203, and the mold 205 are brought intocontact with each other in the mold contacting step (see FIGS. 1D and1DA).

When the mold contacting step is performed under the condensable gasatmosphere, the gas filled into a groove portion of the fine pattern isliquefied by a capillary pressure generated by the curable compositions(A1) 202 and (A2) 203, and hence air bubbles disappear. Accordingly, afilling property becomes excellent. The condensable gas may dissolve inthe curable composition (A1) 202 and/or the curable composition (A2)203.

The boiling point of the condensable gas, which is not limited as longas the boiling point is equal to or less than the ambient temperature ofthe mold contacting step, is preferably from −10° C. to 23° C., morepreferably from 10° C. to 23° C. When the boiling point falls within therange, the filling property is more excellent.

The vapor pressure of the condensable gas at the ambient temperature inthe mold contacting step, which is not limited as long as the vaporpressure is equal to or less than a pressure to be applied to thecurable compositions (A1) 202 and (A2) 203 when the mold 205 and thecurable compositions (A1) 202 and (A2) 203 are brought into contact witheach other when impression is performed in the mold contacting step, ispreferably from 0.1 MPa to 0.4 MPa. When the vapor pressure falls withinthe range, the filling property is more excellent. When the vaporpressure at the ambient temperature is more than 0.4 MPa, the followingtendency is observed: an air bubble disappearing effect cannot besufficiently obtained. On the other hand, when the vapor pressure at theambient temperature is less than 0.1 MPa, the following tendency isobserved: decompression is needed and hence an apparatus becomescomplicated.

The ambient temperature in the mold contacting step, which is notparticularly limited, is preferably from 20° C. to 25° C.

Specific examples of the condensable gas include fluorocarbons such as:a chlorofluorocarbon (CFC) such as trichlorofluoromethane; afluorocarbon (FC); a hydrochlorofluorocarbon (HCFC); a hydrofluorocarbon(HFC) such as 1,1,1,3,3-pentafluoropropane (CHF₂CH₂CF₃, HFC-245fa, PFP);and a hydrofluoroether (HFE) such as pentafluoroethyl methyl ether(CF₃CF₂OCH₃, HFE-245mc).

Of those, 1,1,1,3,3-pentafluoropropane (vapor pressure at 23° C.: 0.14MPa, boiling point: 15° C.), trichlorofluoromethane (vapor pressure at23° C.: 0.1056 MPa, boiling point: 24° C.), and pentafluoroethyl methylether are preferred from such a viewpoint that when the ambienttemperature in the mold contacting step is from 20° C. to 25° C., thefilling property is excellent. Further, 1,1,1,3,3-pentafluoropropane isparticularly preferred from the viewpoint of being excellent in safety.

One kind of the condensable gases may be used alone, or two or morekinds thereof may be used as a mixture. In addition, any suchcondensable gas may be mixed with a non-condensable gas such as air,nitrogen, carbon dioxide, helium, or argon, before use. Thenon-condensable gas with which the condensable gas is mixed ispreferably helium from the viewpoint of the filling property. Helium canpermeate the mold 205. Accordingly, when the gases (the condensable gasand helium) in the atmosphere are filled into a groove portion of thefine pattern formed on the mold 205 in the mold contacting step togetherwith the curable composition (A1) 202 and/or the curable composition(A2) 203, the condensable gas liquefies and helium permeates the mold205.

<Light Irradiating Step (4)>

Next, as illustrated in FIG. 2F, a mixture layer obtained by partiallymixing the curable composition (A1) 202 and the curable composition (A2)203 is irradiated with irradiation light 206 through the mold 205. Inmore detail, the curable composition (A1) 202 and/or the curablecomposition (A2) 203 filled into the fine pattern of the mold 205 are/isirradiated with the irradiation light 206 through the mold 205. Thus,the curable composition (A1) 202 and/or the curable composition (A2) 203filled into the fine pattern of the mold 205 are/is cured by theirradiation light 206 to become the cured film 207 having a patternshape.

In this case, the irradiation light 206 with which the curablecomposition (A1) 202 and/or the curable composition (A2) 203 filled intothe fine pattern of the mold 205 are/is irradiated is selected dependingon the sensitive wavelengths of the curable compositions (A1) 202 and(A2) 203. Specifically, it is preferred that UV light having awavelength of 150 nm or more and 400 nm or less, an X-ray, an electronbeam, or the like be appropriately selected and used.

Of those, the irradiation light 206 is particularly preferably UV light.This is because many of the compounds commercially available as curingaids (photopolymerization initiators) have sensitivity to UV light. Inthis case, examples of the light source of UV light include ahigh-pressure mercury lamp, an ultra-high pressure mercury lamp, alow-pressure mercury lamp, a Deep-UV lamp, a carbon arc lamp, a chemicallamp, a metal halide lamp, a xenon lamp, a KrF excimer laser, an ArFexcimer laser, and a F₂ excimer laser. Of those, an ultra-high pressuremercury lamp is particularly preferred. In addition, the number of thelight sources to be used may be one or two or more. Further, the entiresurface of the curable composition (A1) 202 and/or the curablecomposition (A2) 203 filled into the fine pattern of the mold 205 may beirradiated with light, or a part of the surface thereof may beirradiated with light.

In addition, the light irradiation may be performed on an entire regionon the substrate 201 intermittently a plurality of times, or may becontinuously performed on the entire region. Further, the following maybe performed: a partial region A is irradiated with the light in a firstirradiating process, and a region B different from the region A isirradiated with the light in a second irradiating process.

<Releasing Step (5)>

Next, the cured film 207 having a pattern shape and the mold 205 arereleased from each other. In this step (releasing step), as illustratedin FIG. 2G, the cured film 207 having a pattern shape and the mold 205are released from each other, and hence the cured film 207 having apattern shape serving as the reverse pattern of the fine pattern formedon the mold 205, the film being formed in the step (4) (lightirradiating step), is obtained in an independent state. A cured filmremains in a groove portion of the grove/land pattern of the cured film207 having a pattern shape, and the film is called a remaining film 108(see FIG. 1FA).

When the mold contacting step is performed under the condensable gasatmosphere, the condensable gas vaporizes in association with areduction in pressure of the interface at which the cured film 207 andthe mold 205 are in contact with each other at the time of the releaseof the cured film 207 and the mold 205 in the releasing step. Thus, areducing effect on the release force serving as a force needed forreleasing the cured film 207 and the mold 205 from each other tends tobe exhibited.

A method of releasing the cured film 207 having a pattern shape and themold 205 from each other is not particularly limited as long as part ofthe cured film 207 having a pattern shape is not physically damaged atthe time of the release, and various conditions and the like are alsonot particularly limited. For example, the following may be performed:the substrate 201 (substrate to be processed) is fixed and the mold 205is peeled by being moved so as to recede from the substrate 201.Alternatively, the following may be performed: the mold 205 is fixed andthe substrate 201 is peeled by being moved so as to recede from the mold205. Alternatively, both the substrate 201 and the mold 205 may bepeeled from each other by being pulled in directions diametricallyopposite to each other.

A cured film 207 having a desired groove/land pattern shape (patternshape associated with the groove/land shape of the mold 205) at adesired position can be obtained by a series of steps (productionprocess) including the step (1) to the step (5).

The method of producing a film having a pattern shape of this embodimentenables the following: the curable composition (A1) 202 is collectivelylaid on entire surface of the substrate 201 in the step (1), and arepeating unit (shot) including the step (2) to the step (5) isrepeatedly performed on the same substrate a plurality of times. Inaddition, the step (1) to the step (5) may be repeatedly performed onthe same substrate a plurality of times. When the repeating unit (shot)including the step (1) to the step (5) or of the step (2) to the step(5) is repeated a plurality of times, a cured film 207 having aplurality of desired groove/land pattern shapes (pattern shapesassociated with the groove/land shape of the mold 205) at desiredpositions of the substrate 201 (substrate to be processed) can beobtained. In addition, the step (1) to the step (5) may be collectivelyperformed on the entire surface of the substrate 201.

The substrate 201 (substrate to be processed) or the layer to beprocessed on the substrate 201 (substrate to be processed) can beprocessed into a pattern shape by using: the cured film 207 having apattern shape obtained through the step (1) to the step (5), the filmserving as a mask; and a processing method such as etching. In addition,after the layer to be processed has been further formed on the curedfilm 207 having a pattern shape, pattern transfer may be performed byusing a processing method such as etching. Thus, a circuit structurebased on the pattern shape of the cured film 207 having the patternshape can be formed on the substrate 201. Thus, a circuit board to beutilized in a semiconductor element or the like can be produced. Inaddition, an electronic instrument such as a display, a camera, or amedical apparatus, can be formed by connecting the circuit board and,for example, a circuit control mechanism for a circuit board. Examplesof the semiconductor element as used herein include a LSI, a system LSI,a DRAM, a SDRAM, a RDRAM, a D-RDRAM, and a NAND flash.

An optical component can also be obtained by utilizing the cured film207 having a pattern shape obtained through the step (1) to the step (5)as an optical member such as a diffraction grating or a polarizing plate(the case where the film is used as one member of the optical member isincluded). In such case, an optical component having at least thesubstrate 201 and the cured film 207 having a pattern shape on thesubstrate 201 can be obtained.

In addition, a quartz replica of a quartz imprint mold (mold replica)can be produced by: producing the cured film 207 having a pattern shapethrough the use of a quartz substrate as the substrate 201 and throughthe step (1) to the step (5); and performing pattern transfer throughthe use of a processing method such as etching.

[Set of Imprint Pretreatment Coating Material (Curable Composition (A1))and Imprint Resist (Curable Composition (A2))]

Another aspect of the present invention described above is to provide animprint pretreatment coating material (curable composition (A1)) whichforms a liquid film as pretreatment coating on a substrate and promotesspreading of components of liquid droplets consisting of a curablecomposition (A2) in the plane of the substrate when the liquid dropletsare dispensed onto the liquid film.

In other words, the present invention includes the imprint pretreatmentcoating material consisting of a curable composition (A1), which forms aliquid film as pretreatment coating on a substrate and promotesspreading of components of liquid droplets in the plane of the substratewhen the liquid droplets are dispensed onto the liquid film, wherein thecontact angle of the imprint pretreatment coating material except asolvent with respect to a surface of a mold is 10° or less.

It is preferred that the surface tension of the imprint pretreatmentcoating material be higher than the surface tension of the liquiddroplets dispensed onto the liquid film.

Particularly, it is more preferred that the surface tension of acomposition of the components of the imprint pretreatment coatingmaterial except the solvent be higher than the surface tension of acomposition of the components the imprint resist except the solvent.

Due to the above property, when the liquid droplets are dispensed on theliquid film as pretreatment coating on the substrate, spreading of thecomponents of the liquid droplets in the plane of the substrate ispromoted to thereby realize favorable imprint.

Preferably, such the imprint pretreatment coating material is providedas a set with the imprint resist.

That is, such a set fulfills the relation that the surface tension ofthe composition of the components of the imprint pretreatment coatingmaterial except the solvent is higher than the surface tension of thecomposition of the components of the imprint resist except the solventis provided for realizing favorable imprint.

Particularly, it is more preferable that the set fulfills the relationthat the difference between surface tension of the composition of thecomponents of the imprint pretreatment coating material except thesolvent and the surface tension of the composition of the components ofthe imprint resist except the solvent is 1 mN/m or more and 25 mN/m orless.

A further aspect of the present invention is to provide a method ofpretreating a substrate for favorable imprint, the method comprisingcoating the substrate with the imprint pretreatment coating material.

In addition, the present invention further includes a method for forminga pattern on a substrate. In the pattern forming method of the presentinvention, a resist is dispensed dropwise discretely onto a substratecoated with the imprint pretreatment coating material to thereby promotespreading of components of the resist in the plane of the substrate,whereby the time required for imprint processing can be reduced.

EXAMPLES

The present invention is hereinafter described in more detail by way ofExamples, but the technical scope of the present invention is notlimited to Examples to be described below. The terms “part(s)” and “%”to be used below are by weight in all cases unless otherwise stated.

Example 1

(1) Preparation of Curable Composition (A1-1)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-1) of Example 1.

(1-1) Component (a1):    9 parts by weight 94 parts by weight in total   Isobornyl acrylate (manufactured by Kyoeisha Chemical    Co., Ltd.,trade name: IB-XA):    Benzyl acrylate (manufactured by Osaka Organic  38 parts by weight Chemical Industry Ltd., trade name: V#160):   Neopentyl glycol diacrylate (manufactured by Kyoeisha   47 parts byweight Chemical Co., Ltd., trade name: NP-A):    (1-2) Component (b1):   3 parts by weight in total Irgacure 369 (manufactured by BASF):    3parts by weight (1-3) Component (c1):    0 parts by weight in total Thecomponent (c1) was not added. (1-4) Component (d1) 33000 parts by weight33000 parts by weight in total Propylene glycol monomethyl ether acetate(manufactured by Tokyo Chemical Industry Co., Ltd., abbreviation:PGMEA):

(2) Measurement of Surface Tension of Curable Composition (A1-1)

The surface tension of a composition of the components of the curablecomposition (A1-1) except the component (d1) serving as a solvent at 25°C. was measured with an automatic surface tension meter DY-300(manufactured by Kyowa Interface Science Co., Ltd.) by a plate methodinvolving using a platinum plate. As a result, the surface tension was32.7 mN/m. The measurement was performed under the conditions of anumber of times of the measurement of 5 and a prewet immersion distanceof the platinum plate of 0.35 mm. The first measured value was excluded,and the average of the second to fifth measured values was defined asthe surface tension.

(3) Measurement of Contact Angle of Curable Composition (A1-1) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-1) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured with an automatic static contact angle measuringapparatus Dropmaster 300 (manufactured by Kyowa Interface Science Co.,Ltd.). As a result, the contact angle was 3.3°. The contact angle is avalue 10 seconds after the curable composition has been dispenseddropwise onto the substrate. In addition, the surface of quartz issubjected to UV/ozone cleaning with a UV irradiation apparatus(UVE-110-1H) for 30 minutes.

(4) Preparation of Curable Composition (A2-1)

A component (a2), a component (b2), a component (c2), and a component(d2) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A2-1) of Example 1.

(4-1) Component (a2):   9 parts by weight 94 parts by weight in total  Isobornyl acrylate (manufactured by Kyoeisha Chemical   Co., Ltd., tradename: IB-XA):   Benzyl acrylate (manufactured by Osaka Organic  38 partsby weight Chemical Industry Ltd., trade name: V#160):   Neopentyl glycoldiacrylate (manufactured by Kyoeisha  47 parts by weight Chemical Co.,Ltd., trade name: NP-A): (4-2) Component (b2):   3 parts by weight intotal Irgacure 369 (manufactured by BASF):   3 parts by weight (4-3)Component (c2): 1.1 parts by weight in total Pentadecaethyleneglycolmono 1H,1H,2H,2H,- 1.1 parts by weight perfluorooctyl ether(F(CF2)6CH2CH2(OCH2CH2)15OH) (manufactured by DIC Corporation,abbreviation: DEO-15): (4-4) Component (d2):   0 parts by weight intotal

The component (d2) was not added.

(5) Measurement of Surface Tension of Curable Composition (A2-1)

The surface tension of the curable composition (A2-1) was measured bythe same method as that of the curable composition (A1-1). As a result,the surface tension was 29.1 mN/m.

(6) Photo-Nanoimprint Process

A film of the curable composition (A1-1) having a thickness of fromabout 5 nm to about 10 nm can be obtained by applying the curablecomposition (A1-1) onto a silicon substrate with a spin coater.

One-picoliter droplets of the curable composition (A2-1) can be arrangeddiscretely on the film of the curable composition (A1-1) by using aninkjet method. A droplet amount is set to, for example, such an amountthat the average thickness of a cured film becomes about 50 nm. At thistime, the surface tension of the curable composition (A1-1) arranged inthe lower layer is higher than the surface tension of the curablecomposition (A2-1) dispensed dropwise in the upper layer, and hence theMarangoni effect is expressed and the expansion (prespread) of thedroplets of the curable composition (A2-1) is quick.

In addition, the contact angle of the curable composition (A1-1) withrespect to the surface of the mold is smaller than 10°. Accordingly,even in a portion where the curable composition (A1-1) arranged in thelower layer is brought into direct contact with the surface of the mold,the curable composition (A1-1) is quickly filled into a mold pattern.

Example 2

(1) Preparation of Curable Composition (A1-2)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-2) of Example 2.

(1-1) Component (a1): 94 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-2) Component (b1): 3 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-3) Component (c1):   0.9 parts by weight in total 0.9 parts by weightin total Polyoxyethylene stearyl ether (EO 15 mol adduct) (manufacturedby Aoki Oil Industrial Co., Ltd., trade name: BLAUNON SR-715) (1-4)Component (d1):  33000 parts by weight in total

The same formulation as that of Example 1 was adopted.

(2) Measurement of Surface Tension of Curable Composition (A1-2)

The surface tension of a composition of the components of the curablecomposition (A1-2) except the component (d1) serving as a solvent wasmeasured in the same manner as in Example 1. As a result, the surfacetension was 30.7 mN/m.

(3) Measurement of Contact Angle of Curable Composition (A1-2) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-2) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured in the same manner as in Example 1. As a result,the contact angle was 5.1°.

(4) Curable Composition (A2-2)

The same composition as that of Example 1 was used as a curablecomposition (A2-2).

(5) Measurement of Surface Tension of Curable Composition (A2-2)

The surface tension of the curable composition (A2-2) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

As in Example 1, the surface tension of the curable composition (A1-2)arranged in the lower layer is higher than the surface tension of thecurable composition (A2-2) dispensed dropwise in the upper layer, andhence the Marangoni effect is expressed and the expansion (prespread) ofthe droplets of the curable composition (A2-2) is quick.

In addition, the contact angle of the curable composition (A1-2) withrespect to the surface of the mold is smaller than 10°. Accordingly,even in a portion where the curable composition (A1-2) arranged in thelower layer is brought into direct contact with the surface of the mold,the curable composition (A1-2) is quickly filled into a mold pattern.

(Example 3)

(1) Preparation of Curable Composition (A1-3)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-3) of Example 3.

(1-1) Component (a1): 94 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-2) Component (b1):    3 parts by weight 3 parts by weight in totalIrgacure 651 (manufactured by BASF): (1-3) Component (c1):   1.6 partsby weight in total 1.6 parts by weight in total polyoxyethylene stearylether (EO 30 mol adduct) (manufactured by Aoki Oil Industrial Co., Ltd.,trade name: BLAUNON SR-730) (1-4) Component (d1):  33000 parts by weightin total

The same formulation as that of Example 1 was adopted.

(2) Measurement of Surface Tension of Curable Composition (A1-3)

The surface tension of a composition of the components of the curablecomposition (A1-3) except the component (d1) serving as a solvent wasmeasured in the same manner as in Example 1. As a result, the surfacetension was 33.2 mN/m.

(3) Measurement of Contact Angle of Curable Composition (A1-3) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-3) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured in the same manner as in Example 1. As a result,the contact angle was 3.7°.

(4) Curable Composition (A2-3)

The same composition as that of Example 1 was used as a curablecomposition (A2-3).

(5) Measurement of Surface Tension of Curable Composition (A2-3)

The surface tension of the curable composition (A2-3) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

As in Example 1, the surface tension of the curable composition (A1-3)arranged in the lower layer is higher than the surface tension of thecurable composition (A2-3) dispensed dropwise in the upper layer, andhence the Marangoni effect is expressed and the expansion (prespread) ofthe droplets of the curable composition (A2-3) is quick.

In addition, the contact angle of the curable composition (A1-3) withrespect to the surface of the mold is smaller than 10°. Accordingly,even in a portion where the curable composition (A1-3) arranged in thelower layer is brought into direct contact with the surface of the mold,the curable composition (A1-3) is quickly filled into a mold pattern.

(Comparative Example 0)

(1) to (3) Curable Composition (A1-0′) In Comparative Example 0, thecurable composition (A1) was not used.

(4) Curable Composition (A2-0′)

The same composition as that of Example 1 was used as a curablecomposition (A2-0′).

(5) Measurement of Surface Tension of Curable Composition (A2-0′)

The surface tension of the curable composition (A2-0′) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

When the curable composition (A2-0′) is directly dispensed dropwise ontothe surface of a substrate serving as a solid surface, the Marangonieffect is not expressed. In other words, a prespread promoting effect isnot obtained and hence the expansion of the droplets of the curablecomposition (A2-0′) is slower than that of each of Examples of thepresent invention.

Comparative Example 1

(1) Preparation of Curable Composition (A1-1′)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-1′) of Comparative Example 1.

(1-1) Component (a1): 61.6 parts by weight 94 parts by weight in totalIsobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., tradename: IB-XA): (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl acrylate   10parts by weight (manufactured by Osaka Organic Chemical Industry Ltd.,trade name: MEDOL-10): 1,6-hexanediol diacrylate (manufactured by Osaka22.4 parts by weight Organic Chemical Industry Ltd., trade name:Viscoat#230): (1-2) Component (b1):   3 parts by weight 3 parts byweight in total Irgacure 651 (manufactured by BASF): (1-3) Component(c1):   0 parts by weight in total

The component (c) was not added.

(1-4) Component (d1): 33000 parts by weight in total

The same formulation as that of Example 1 was adopted.

(2) Measurement of Surface Tension of Curable Composition (A1-1′)

The surface tension of a composition of the components of the curablecomposition (A1-1′) except the component (d1) serving as a solvent wasmeasured in the same manner as in Example 1. As a result, the surfacetension was 28.1 mN/m.

(3) Measurement of Contact Angle of Curable Composition (A1-1′) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-1′) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured in the same manner as in Example 1. As a result,the contact angle was 3.6°.

(4) Curable Composition (A2-1′)

The same composition as that of Example 1 was used as a curablecomposition (A2-1′).

(5) Measurement of Surface Tension of Curable Composition (A2-1′)

The surface tension of the curable composition (A2-1′) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

As in Example 1, the surface tension of the curable composition (A1-1′)arranged in the lower layer is lower than the surface tension of thecurable composition (A2-1′) dispensed dropwise in the upper layer, andhence the Marangoni effect is not expressed and the expansion of thedroplets of the curable composition (A2-1′) is slower than those of theExamples.

In addition, the contact angle of the curable composition (A1-1′) withrespect to the surface of the mold is smaller than 10°. Accordingly,even in a portion where the curable composition (A1-1′) arranged in thelower layer is brought into direct contact with the surface of the mold,the curable composition (A1-1′) is quickly filled into a mold pattern.

Comparative Example 2

(1) Preparation of Curable Composition (A1-2′)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-2′) of Comparative Example 2.

(1-1) Component (a1): 94 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-2) Component (b1): 3 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-3) Component (c1):   1.1 parts by weight 1.1 parts by weight in totalPentadecaethyleneglycol mono 1H,1H,2H,2H,- perfluorooctyl ether(F(CF2)6CH2CH2(OCH2CH2)15OH) (manufactured by DIC Corporation,abbreviation: DEO-15): (1-4) Component (d1):  33000 parts by weight intotal

The same formulation as that of Example 1 was adopted.

(2) Measurement of Surface Tension of Curable Composition (A1-2′)

The surface tension of a composition of the components of the curablecomposition (A1-2′) except the component (d1) serving as a solvent wasmeasured in the same manner as in Example 1. As a result, the surfacetension was 29.1 mN/m.

(3) Measurement of Contact Angle of Curable Composition (A1-2′) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-2′) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured in the same manner as in Example 1. As a result,the contact angle was 22.9°.

(4) Curable Composition (A2-2′)

The same composition as that of Example 1 was used as a curablecomposition (A2-2′).

(5) Measurement of Surface Tension of Curable Composition (A2-2′)

The surface tension of the curable composition (A2-2′) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

As in Example 1, the surface tension of the curable composition (A1-2′)arranged in the lower layer is equal to the surface tension of thecurable composition (A2-2′) dispensed dropwise in the upper layer, andhence the Marangoni effect is not expressed and the expansion of thedroplets of the curable composition (A2-2′) is slower than those of theExamples.

In addition, the contact angle of the curable composition (A1-2′) withrespect to the surface of the mold is larger than 10°. Accordingly, evenin a portion where the curable composition (A1-2′) arranged in the lowerlayer is brought into direct contact with the surface of the mold, ittakes longer time to fill the curable composition (A1-2′) into a moldpattern in comparison with the Examples.

Comparative Example 3

(1) Preparation of Curable Composition (A1-3′)

A component (a1), a component (b1), a component (c1), and a component(d1) described below were blended, and the blend was filtered with a0.2-micrometer filter made of ultrahigh-molecular weight polyethylene toprepare a curable composition (A1-3′) of Comparative Example 3.

(1-1) Component (a1): 94 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-2) Component (b1): 3 parts by weight in total

The same formulation as that of Example 1 was adopted.

(1-3) Component (c1):   1.1 parts by weight in totalPentadecaethyleneglycol-methyl-1H,1H,2H,2H,-   1.1 parts by weightperfluorooctyl ether (F(CF2)6CH2CH2(OCH2CH2)15-CH3) (manufactured byNARD, abbreviation: DEO-15Me): (1-4) Component (d1):  33000 parts byweight in total

The same formulation as that of Example 1 was adopted.

(2) Measurement of Surface Tension of Curable Composition (A1-3′)

The surface tension of a composition of the components of the curablecomposition (A1-3′) except the component (d1) serving as a solvent wasmeasured in the same manner as in Example 1. As a result, the surfacetension was 30.7 mN/m.

(3) Measurement of Contact Angle of Curable Composition (A1-3′) withRespect to Surface of Mold

A contact angle between a composition of the components of the curablecomposition (A1-3′) except the component (d1) serving as a solvent andthe surface of quartz serving as a parent material for the mold of thisexample was measured in the same manner as in Example 1. As a result,the contact angle was 24.1°.

(4) Curable Composition (A2-3′)

The same composition as that of Example 1 was used as a curablecomposition (A2-3′).

(5) Measurement of Surface Tension of Curable Composition (A2-3′)

The surface tension of the curable composition (A2-3′) was 29.1 mN/m assame as that of Example 1.

(6) Photo-Nanoimprint Process

As in Example 1, the surface tension of the curable composition (A1-3′)arranged in the lower layer is higher than the surface tension of thecurable composition (A2-3′) dispensed dropwise in the upper layer, andhence the Marangoni effect is expressed and the expansion (prespread) ofthe droplets of the curable composition (A2-3′) is quick.

In addition, the contact angle of the curable composition (A1-3′) withrespect to the surface of the mold is larger than 10°. Accordingly, evenin a portion where the curable composition (A1-3′) arranged in the lowerlayer is brought into direct contact with the surface of the mold, ittakes longer time to fill the curable composition (A1-3′) into a moldpattern in comparison with the Examples.

Summary of Examples and Comparative Examples

The composition tables of Examples 1 to 3 and Comparative Examples 0 to3 are collectively shown in Table and Table 2, and the effects of theinvention are collectively shown in Table 3.

TABLE 1 Composition table of curable composition (A1) (part(s) byweight) Component Component Component Component (a) (b) (c) (d) Example1 IB-XA (9) I.369(3) Absent PGMEA Example 2 V#160 (38) SR-715 (33000)NP-A (47) (0.9) Example 3 I.651 (3) SR-730 (1.6) Comparative (Curablecomposition (A1) was not used) Example 0 Comparative IB-XA (61.6)I.651(3) Absent PGMEA Example 1 MEDOL-10 (33000) (10) V#230(22.4)Comparative IB-XA(9) I.369(3) DEO-15 Example 2 V#160 (38) (1.1)Comparative NP-A (47) DEO-15Me Example 3 (1.1)

TABLE 2 Composition table of curable composition (A2) (part(s) byweight) Component Component Component Component (a) (b) (c) (d) Example1 IB-XA (9) I.369 (3) DEO-15 (1.1) Absent Example 2 V#160 (38) Example 3NP-A (47) Comparative Example 0 Comparative Example 1 ComparativeExample 2 Comparative Example 3

TABLE 3 Effects of invention Composition Composition (A1) (A2) SurfaceContact Surface tension Angle tension (mN/m) (°) (mN/m) Prespread fillExample 1 32.7 3.3 29.1 fast standard Example 2 30.7 5.1 fast fastExample 3 33.2 3.7 fast fast Comparative (Composition (A1) standard slowExample 0 was not used) Comparative 28.1 3.6 slow fast Example 1Comparative 29.1 22.9 slow slow Example 2 Comparative 30.7 24.1 fastslow Example 3

In Table 3, the evaluation of the prespread was a relative evaluationwith reference to Comparative Example 0. In other words, the prespreadwas evaluated as being “fast” when its speed was faster than that ofComparative Example 0, and the prespread was evaluated as being “slow”when its speed was on the same level with that of Comparative Example 0or slower than that of Comparative Example 0. The prespread of each ofExamples 1 to 3 and Comparative Example 3 is faster than that ofComparative Example 0, in other words, the case where the curablecomposition (A1) is not used by virtue of the Marangoni effect.

In Table 3, the evaluation of the fill was a relative evaluation withreference to Example 1. In other words, the fill was evaluated as being“fast” when its rate was comparable to that of Example 1, and the fillwas evaluated as being “slow” when its rate was slower than that ofExample 1.

It has been shown from the foregoing that when the method of thisembodiment is used, a photo-nanoimprint pattern can be formed at highthroughput.

While the present invention has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

What is claimed is:
 1. A pattern forming method, comprising in thefollowing order: a first laying step (1) of arranging a layer formed ofa curable composition (A1) containing at least a component (a1) servingas a polymerizable compound on a surface of a substrate; a second layingstep (2) of dispensing droplets of a curable composition (A2) containingat least a component (a2) serving as a polymerizable compound dropwisediscretely onto the layer formed of the curable composition (A1) to laythe droplets; a mold contacting step (3) of sandwiching a mixture layerobtained by partially mixing the curable composition (A1) and thecurable composition (A2) between a mold having a pattern and thesubstrate; a light irradiating step (4) of irradiating the mixture layerwith light from the side of the mold to cure the layer; and a releasingstep (5) of releasing the mold from the mixture layer after the curing,a contact angle of a composition of components of the curablecomposition (A1) except a solvent with respect to a surface of the moldbeing 10° or less.
 2. A pattern forming method according to claim 1,wherein the layer of the curable composition (A1) comprises a liquidfilm, and at least part of the curable composition (A1) is brought intodirect contact with the mold.
 3. A pattern forming method according toclaim 1, wherein a surface tension of a composition of components of thecurable composition (A1) except a solvent is higher than a surfacetension of a composition of components of the curable composition (A2)except a solvent.
 4. A pattern forming method according to claim 1,wherein a viscosity of a composition of components of the curablecomposition (A1) except a solvent is 1 mPa·s or more and 1,000 mPa·s orless, and a viscosity of a composition of components of the curablecomposition (A2) except a solvent is 1 mPa·s or more and 12 mPa·s orless.
 5. A pattern forming method according to claim 1, wherein amaterial for a surface of the mold comprises quartz.
 6. A patternforming method according to claim 1, wherein the mold contacting step isperformed under an atmosphere containing a condensable gas.
 7. A patternforming method according to claim 6, wherein the second laying step isperformed under an atmosphere of a mixed gas containing the condensablegas and a non-condensable gas.
 8. A pattern forming method according toclaim 7, wherein the non-condensable gas is helium.
 9. A pattern formingmethod according to claim 6, wherein the condensable gas is1,1,1,3,3-pentafluoropropane.
 10. A method of producing a processedsubstrate, comprising the pattern forming method of claim
 1. 11. Amethod of producing an optical component, comprising the pattern formingmethod of claim
 1. 12. A method of producing a quartz mold replica,comprising the pattern forming method of claim
 1. 13. A pattern formingmethod according to claim 1, wherein the pattern comprises a nanosizegroove/land pattern based on a cured product of the mixture of thecurable compositions (A1) and (A2).
 14. An imprint pretreatment coatingmaterial consisting of a curable composition (A1) which forms a liquidfilm as pretreatment coating on a substrate and promotes spreading ofcomponents of liquid droplets in the plane of the substrate when theliquid droplets are dispensed onto the liquid film, wherein the contactangle of a composition of components of the imprint pretreatment coatingmaterial except a solvent with respect to a surface of a mold is 10° orless.
 15. An imprint pretreatment coating material according to claim14, wherein the surface tension of the imprint pretreatment coatingmaterial is higher than the surface tension of liquid droplets dispensedonto the liquid film of the imprint pretreatment coating material.
 16. Aset containing the imprint pretreatment coating material of claim 14 andan imprint resist consisting of a curable composition (A2) to bedispensed on the substrate coated with the imprint pretreatment coatingmaterial.
 17. A set according to claim 16, wherein a surface tension ofa composition of components of the imprint pretreatment coating materialexcept a solvent is higher than a surface tension of a composition ofcomponents of the imprint resist except a solvent.
 18. An imprint resistto be used for the set of claim
 17. 19. A pretreatment method forperforming imprint processing of a substrate with arranging a curablecomposition on the substrate, comprising coating a substrate with theimprint pretreatment coating material of claim
 14. 20. A pattern formingmethod for forming a pattern on a substrate, comprising dispensing aresist dropwise discretely on a substrate coated with the imprintpretreatment coating material of claim 14.